The use of a polyvalent cation-organic phosphonic acid complex as a bleaching agent

ABSTRACT

In a method of developing, bleaching and fixing an exposed silver halide photographic material, the improvement comprising bleaching the silver halide photographic material with a bleaching solution containing a polyvalent cation-organic phosphonic acid complex as the bleaching agent.

United States Patent Shimamura et al.

[ Dec. 23, 1975 THE USE OF A POLYVALENT CATION-ORGANIC PHOSPHONIC ACID COMPLEX AS A BLEACHING AGENT Inventors: Isao Shimamura; Haruhiko Iwano,

both of Minami Ashigara, Japan Assignee: Fuji Photo Film Co., Ltd., Minami Ashigara, Japan Filed: July 8, 1974 Appl. No.: 486,737

Foreign Application Priority Data July 7, 1973 Japan 48-76842 US. Cl. 96/60 Int. Cl. G03C 5/32 Field of Search 96/60, 60 BF [56] References Cited UNITED STATES PATENTS 3,615,508 10/1971 Stephen et a1. 96/60 BF 3,706,561 12/1972 Mowrey et al. 96/60 R Primary Examiner-David Klein Assistant ExaminerJudson R. I-Iightower Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn 8L Macpeak [57] ABSTRACT plex as the bleaching agent.

18 Claims, No Drawings THE'USE OF A POLYVALENT CATION-ORGANIC PHOSPHONIC ACID COMPLEX AS A BLEACHING AGENT BACKGROUND OF THE INVENTION l. Field of the Invention Thisinvention relates to a method for processing photographic materials, and more precisely, to a method for bleaching of a developed silver halide photographic emulsion layer.

2. Description of the Prior Art In .the processing of some kinds of silver halide photographic materials a step for removal of developed silver from the silver halide emulsion layer (the socalled bleaching step) is included. For example, in the processing of color photographic materials such as color negative films, color .reversaLfilms and color papers, a step for the removal of silver images formed in color development is carried out in order to retain only color images formed in the color development; and analogously, in the processing of black-white reversalphotographic materials a step for the removal of silver images formed in an initial exposure and development is carried out for thepurpose oflformation of positive images.

Ferricyanides and iron-aminopolycarboxylic acid complexes, for example, are known as bleaching agents used in these steps. These conventional bleaching agents, however, are not completelysatisfactory with respect to both non-toxicity and bleaching ability, and therefore, recently, discovery of other practical photographic bleaching agents 7 as well as photographic bleaching methods have been desired.

SUMMARY OF THE INVENTION An object of this invention is to provide a photographic bleaching methodwhere a less toxic bleaching agent of a high bleaching rate is used.-

, Another object of this invention is to provide a method'of formation of color photographic images at a much reduced bleaching time. 1

Still another object of this invention is to provide a method for processing color photographic materials which does not give rise to pollution problems.

' These objects of this invention are achieved by the use of a bleaching solution containing a polyvalent cation-organic phosphonicacid complex as the bleaching agent. More precisely, the method of this invention comprises processing an exposed and developed silver halide emulsion layer with a bleaching solution containing a polyvalent cation-organic phosphonic acid complex as the bleaching agent.

DETAILED DESCRIPTION OF THE INVENTION As described above, a method for processing photographic materials where a polyvalent cationaminopolycarboxylic acid complex is used as a bleaching component is already known. The method of this invention isdifferent from this conventional method in the use of an organic phosphonic acid in place of the aminopolycarboxylic acid, which is an important factor. Accordingly, the polyvalent cations in the present invention can be interpreted as having the same meanings as those of known polyvalent cations. Various kinds of polyvalent cations which can form complexes are known in the chemical field, and'one skilled in the art can easily select these cations. Of thepolyvalent benzothiazoylmethyl cations Fe(IlI), Co, Ni and Cu(II) are particularly useful in the method of this invention.

On the other hand, organic phosphonic acids are also well known, and 'aminopolymethylene phosphonic acids (or water-soluble salts thereof) are especially advantageous. Aminopolymethylene phosphonic acids can be represented by the following general formula (I):

where M represents a hydrogen atom or a cation which 1 or o-acetamidobenzyl group, especially an aralkyl group having 7 to 9 carbon atoms), an alicyclic group (e.g., a cyclohexyl or cyclopentyl group), or a heterocyclic group (e.g., a pyrrolidylmethyl, pyrrolidylbutyl,

or group), and R (especially when representing an alkyl group) can be substituted with a hydroxyl group, an alkoxy group (e.g. a methoxy or ethoxy group), a halogen atom (e.g., a chlorine atom), PO M Cl-l- PO M or N(C l-I PQ M where M has the same meaning as described above.

Representative examples'of these phosphonic acids of the general formula (I) are given below.

Ethylenediamine-N,N,N',N'-tetramethylene phonic acid Nitrilo-N,N,N-trimethylene phosphonic acid 1 ,2-Cyclohexanediamine-N,N,N ',N'-tetramethylene phosphonic acid o-Carboxyaniline-N,N-dimethylene phosphonic acid Propylamine-N,N-dimethylene phosphonic acid 4-(N-Pyrrolidino)butylamine-N,N-bis(methylene phosphonic acid) l ,3-Diaminopropanol-N,N,N',Nfftetramethylene phosphonic acid l,3-Propanediamine-N,N,N',N'- tetra methylene phosphonic acid l,-l lexanediamine-N,N,N,N-tetramethylene phos- 'phonicacid I o-Acetamidobenzylamine-N,N dimethylene phonic acid o-Toluidine-N,N dimethylene phosphonic acid ,Z-Pyridylamine-N,N dimethylene phosphonic acid Other examples of organic phosphonic acids are compounds represented by the following general formula (II): I

2 a a 2)2 where R represents a hydrogen atom, or an alkyl, aralkyl, alicyclic or heterocyclic group which is defined above, 01' -PO M and R represents a hydrogen atom, a hydroxyl group or an alkyl group, or the above defined substituted alkyl group or --P0 M where M has the same meaning as described above. Representative examples of compounds of the above general formula (II) are given below.

l I-Iydroxyethylidene-l ,1 -diphosphonic acid Ethylidinel ,1 ,l-triphosphonic acid phosphosl-l-Iydro'xy-2-phenylethylidene-l ,l-diphosphonic acid These organic phosphonic acids are described in US. Pat. No. 3,617,282.

tetrahydroquinolylmethyl The bleaching solution used in the present invention contains as a bleaching agent the above specified polyvalent cation-organic phosphonic acid complex. The amount of this complex is generally about 20 to 200 g, preferably 50 to 150 g, per 1 liter of the bleaching solution. The lower limit of the amount of complex depends upon the bleaching ability thereof, and the upper limit thereof mainly depends upon factors such as solubility and economics. Accordingly, the upper limit of the amount of the complex can be extended further by the use of an appropriate dissolution aid, and so, the upper limit thereof is not limited to within the above mentioned scope. In the present invention it is only important that the bleaching solution contain the above described complex, and therefore, the method of addition thereof can be broadly. In general, a convenient method comprises adding a complex which was previously prepared to an aqueous solution, but apart from this, it also is possible to form the complex in an aqu'eoussolution by adding a salt of poly-valent cation and an organic phosphonicacid to the aqueous solution. In the latter case, the amount of both compounds ;preferably 50to 200 g, per 1 liter'of the bleaching solution.

In addition, the bleaching solution of this invention can further contain other additives known in this technical field as being capable of being added to a bleaching solution or a bleaching-fixation solution. Such additives include nitrates such as sodium nitrate, sulfites such as sodium sulfite, mercapto compounds such as mercaptotriazole, pH buffers such'as borates, oxalates,

- acetates, carbonates, phosphates, stain-inhibitors such as formamidinosulfinic acid, polyamine compounds as described, for example, in US. Pat. No. 3,578,454, alkylamine compounds as described, for example, in

'U.S. Pat. No. 3,578,453, polyethyleneoxides as described, for example, in German Pat. No. 966,410, and nitrogen containing heterocyclic compounds as described, for example, in German Pat. No. 1,290,812.

A suitable pH for the bleaching solution of this invention is a pH of about 3 to 8, preferably 5 to 7.

The method of this invention comprises the individual steps of development, bleaching and fixation. The

development is generally color development, but development also means black-white development or blackwhite development and color development. the abovedescribed three steps need not be necessarily carried out without interruption, and other additional steps can be carried out before and after each of these steps. Such additional steps include subjecting the photographic material to a fixation bath, an image stabilization bath, a hardening bath, a neutralization bath, a water-washing including rinsing), etc., and, as the case may be, the bleaching and fixation step can further be included.

The color developer used in the present invention is an alkaline aqueous solution of a known aromatic primary amine color developing agent, and preferably contains 1 g/liter or more, or as the case may be, less than 1 g/liter, of benzyl alcohol. Representative examples of color developing agents are phenylenediamine derivatives such as N,N-diethyl-p-phenylenediamine sulfate, 4-amino-N-ethyl-N-B-hydroxyethylaniline sulfate, 3-methyl-4-amino-N-ethyl-B-methanesulfoamidoethylaniline-sesquisulfatemonohydrate, 3-methyl-4- amino-N-ethyl-N-fl-hydroxyethylaniline sulfate, 3- methyl-4 amino-N,N-diethylaniline chloride, etc. In addition, the color developer can contain known developer additives such as alkali metal sulfites, carbonates, bisulfites, bromides, iodides as well as anti-fogging agents, development accelerating agents and solvents such as diethylene glycol.

When color photographic material which do not contain a color coupler are developed, the color developer contains a color coupler (for example, as described in US. Pat. Nos. 2,252,718; 2,592,243 and 2,590,970).

On the other hand, when the method of this invention is applied to black-white development, an alkaline aqueous solution is used as a developer, containing developing agents such as the dihydroxybenzenes (e.g., hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichloro-hydroquinone, 2,5- dimethyl-hydroquinone), the 3-pyrazolidones (e.g., l-phenyl-3-pyrazolidone, l-phenyl-4,4-dimethyl-3- pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, l-phenyl-5-methyl-3-pyrazolidone), the aminophenols (e.g., o-ami nophenol, p-aminophenol, N-methyl-o-aminophenol, N-rnethyl-p-aminophenol, 2,4-diaminophenol), pyrogallol, ascorbic acid, the l-arylaminopyrazolines (e.g., 1-(p-hydroxyphenyl)-3- aminopyrazoline, 1 -(p-methylaminophenyl) 3- aminopyrazoline, l-(p-aminophenyl)-3-aminopyrazoline, l{p-amino-m-methylphenyl)-3-aminopyrazoline) or amixture thereof. The pH of each of these blackwhite developers and color developers is about 9 to 13, preferably 10 to 12.5.

In the fixation step carried out after the bleaching step, each and every conventional fixing solution can be used. A suitable description thereof appears in US. Pat. No. 3,582,322. More precisely, about 50 to 200 g/liter or so of ammonium, sodium or potassium thiosulfate can be used as a fixing agent, and additionally, a stabilizer such as sulfite or metabisulfite, a hardening agent such as potassium alum, and a pH buffer such as acetate or borate can also be contained in the fixing solution. The fixing solution has a pH value of about 3 to 10.

Photographic materials to which the method of this invention can be applied contain at least one silver halide emulsion layer. The silver halide emulsion is prepared by dispersing a silver halide such as silver chloride, silver iodide, silver bromide, silver bromochloride, silver bromoiodide, or silver bromoiodochloride, in a hydrophilic colloid (binder).

Representative examples of hydrophilic colloids are,

for example, galatin, colloidal albumin, casein, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, saccharide derivatives such as agar, sodium alginate and starch derivatives, and synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyacrylic acid copolymers,

polyacrylamide and derivatives thereof. If desired, a compatible mixture of two or more of these colloids can be used. Of these colloids the most common one is gelatin, and a part or all of the gelatin can be replaced by synthetic high molecular weight substances. In addition, the gelatin can also be substituted by the so-called gelatin derivatives (that is, those prepared by treating the functional groups contained in the molecule such as amino groups, imino groups, hydroxy groups or carboxyl groups, with an agent having one group capable of reacting with these functional groups) or by gelatin graft-polymers grafted with molecular chains of other high molecular weight substances. Representative examples of agents for preparing gelatin derivatives are, for example, the isocyanates, acid chlorides and acid anhydrides as described in U.S. Pat. No. 2,614,928; the acid anhydrides described in U.S. Pat. No. 3,118,766; the bromoacetic acids described in Japanese Pat. Publication No. 5514/64; the phenylglycidylethers described in Japanese Pat. Publication No. 26845/67; the vinylsulfone compounds described in U.S. Pat. No. 3,132,945; the N-allylvinyl-sulfonamides described in British Pat. No. 861,414; the maleinimide compounds described in U.S. Pat. No. 3,186,846; the acrylonitriles described in U.S. 'Pat. No. 2,594,293; the polyalkyleneoxides described in U.S. Pat. No. 3,312,553; the epoxy compounds described in Japanese Pat. Publication No. 26845/67; the acid esters described in U.S. Pat. No. 2,763,639; and the alkanesultones described in British Pat. No. 1,033,189. Regarding the high molecular weight substances (i.e., the branch component) which can be grafted on gelatin, a number of substances are disclosed, for example, in U.S. Pat. No. 2,763,625, No. 2,831,767 and No. 2,956,884, and P01- ymer Letters 5, 594 (1967), Phot. Sci. Eng, 9, 148 (1965), and J. of Polymer Sci. A-l, 9, 3199 (1971), and in addition, a broad range of polymers or copolymers of the so-called vinyl monomers such as acrylic acid and methacrylic acid or esters, amides and nitriles thereof as well as styrene can also be used as such a substance. In particular, hydrophilic vinyl polymers which are compatible with gelatin to some degree, such as the polymers or copolymers of acrylic acid, acrylamide, methacrylamide, hydroxyalkyl acrylate or hydroxyalkyl methacrylate, are especially preferred.

Silver halide emulsions can be prepared using conventional techniques which are generally well known in this technical field (e.g., the single-jet process, the double-jet process, the control-jet process) where a water-soluble silver salt (e.g., silver nitrate) and a water-soluble halide are admixed in the presence of water and the hydrophilic colloid and the mixture is subjected to physical ripening and chemical ripening such as gold sensitization and/or sulfur sensitization. To the silver halide emulsion, spectral sensitizer (e.g. cyanine dyes, merocyanine dyes or mixtures thereof, for example, as disclosed in U.S. Pat. Nos. 2,493,748;

3,694,217; etc.), stabilizers (e.g., 4-hydroxy-6-methyll,3,3a,7-tetrazaindene), sensitizers (e.g., the compounds described in U.S. Pat. No. 3,619,198), anti-fogging agent's (e.g., benzotriazole, S-nitrobenzimidazole, polyethyleneoxide), hardening agents (e.g., aldehyde compounds such as formaldehyde and glyoxal, nonaldehyde compounds such as mucochloric acid and 2-hydr0xy-4,6-dichloro-s-triazine, for example, as de- 3,543,292; etc.) and coating auxiliaries (e.g., saponin, sodium lauryl sulfate, dodecylphenolpolyethyleneoxide ether, hexadecyltrimethylammonium bromide) can be added during the preparation thereof or immediately before the application thereof. The silver halides in the emulsion thus obtained preferably have an average particle size of about 0.2 to 1.5 t.

When the method of this invention is applied to a system where a color coupler is contained in a photographic material (as disclosed in U.S. Pat. Nos. 2,376,679, 2,322,027 and 2,801,171), at least one silver halide emulsion layer can contain a color coupler (i.e., a compound forming a dye after reaction with an oxidation product of a color developing agent). In gen.- eral, each of a cyan, magenta and yellow color coupler is used in color'photography. Suitable examples of color couplers are described as follows: cyan couplers;

U.S. Pat. Nos. 2,474,293; 2,698,794; 3,034,892; 3,253,924; 3,311,476; 3,458,315; 3,582,322; 3,591,383; etc. magenta couplers;

U.S. Pat. Nos. 2,600,788; 2,983,608; 3,006,759; 3,062,653; 3,214,437; 3,253,924; 3,311,476; 3,337,344; 3,419,391; 3,419,808; 3,476,560;

3,582,322; etc.

yellow couplers; v

U.S. Pat. Nos. 3,277,157; 3,415,652; 3,447,928; 3,311,476; 3,408,194; 2,875,057; 3,265,506; 3,409,439; 3,551,157; 3,551,156; 3,582,322; etc. More precisely, a color coupler which hasa naphthol or phenol skeleton and can form an indoaniline dye by coupling is used as a cyan coupler; a color coupler which has active methylene groups and a S-pyrazolone ring structure sleketon is used as a magenta coupler; and a color coupler of a benzoylacetanilide, pivalylacetanilide or acrylacetanilide structure with or without a substituent in the coupling position, is used as a yellow coupler. This is because the bleaching solution of this invention has a sufficient oxidizability to increase the color density.

Repr'esentative of pyrazolone color couplers are those represented by the general formula (III) wherein, R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and R represents an alkyl group, a carbamyl group, an amino group or an amido group. Examples of compounds represented by the above formula are as follows:

1 -p-sec-Amylphenyl-3 -n-amyl-5-pyrazolone 2-Cyanoacetyl-5-(p-sec-amylbenzoylamino)coumarone 7 2-Cyanoacetylcoumaron-5-(N-n-amyl-p-t-amylsulfoanilide) 2-Cyanoacetylcoumaron-5-sulfon-N-n-butylanilide l-p-Laurylphenyl-3 -methyl- -pyrazolone l-l3-Naphthyl-3 -amyl-5 -pyrazolone l-p-Nitrophenyl-3 -n-am yl-5-pyrazolone l-Phenyl-3-acetylamino-5-pyrazolone l-Phenyl-3 -n-valerylamino-5 -pyrazolone l-Phenyl-3-chloroacetylamino-5-pyrazolone l-Phenyl-3-( m-aminobenzoyl)amino-5-pyrazolone l-p-Phenoxyphenyl-3-(p-t-amyloxybenzoyl )amino- S-pyrazolone l-l(2',4 ,6-Trichlorophenyl)-3-benzamido-5-pyrazoone 1-(2',4-Dichlorophenyl)-3-[ 3 '-(2"',4"'-di-t-amylphenoxyacetamido)benzamido]-5-pyrazolone l-(2,4-Dimethyl-6-chlorophenyl)-3-[ 3 '-(2" ',4-dit-amylphenoxyacetamido)benzamido] -5-pyrazolone In addition, the following couplers can also be used: l-(2',4',6'-Trichlorophenyl)-3-(2-chloro-5 '-tetradecaneamidoanilino )-5-pyrazolone l-( 2',4,6'-Trichlorophenyl)-3-{ 2-chloro-5 -[N- 3 2' ,5 -di-t-pentylphenoxy )propyl]sulfamoylanilino}-5-pyrazolone l-(2',4',6-Trichlorophenyl)-3-(2"-chloro-4 '-tetradecyloxy-carbonylanilino)-5-pyrazolone l-( 2 ,6 '-Dichloro-4 '-tetradecyloxycarbonylphenyl 3-( 2,4-dichloroanilino)-5-pyrazolone 1-(2',4,6'-Trichlorophenyl)-3-{2"-chloro-5 "-[2" (3 -t-butyl-4' -hydroxyphenoxy)tetradecaneamido]anilino} -5-pyrazolone 1-(2',4,6'-Trichlorophenyl)-3-(2-chloro-5 '-tetradecaneamidoanilino)-5-pyrazolone l-(2,4',6'-Trichlorophenyl)-3-{3 -[a-2' ",4" '-di-tpentylphenoxy)acetamido]benzamido}-5-pyrazolon-4-yl-benzyl carbonate l-(2',4',6'-Trichlorophenyl)-3- {3 "-[a-( 3 -pentadecylphenoxy)butylamido]benzamido}-5- pyrazolon-4-yl-ethyl carbonate 1-(2',4',6'-Trichlorophenyl)-3-{2"-chloro-5 -[y- (2' 4' '-di-t-pentylphenoxy)propylsulfamoyl- ]anilino}-5-pyrazolon-4-yl-benzyl carbonate in addition, other color couplers as described in British Pat. No. 1,142,553 and US. Pat. Nos. 3,337,344 and 3,582,322 can also be used.

Examples of four-equivalent couplers which form yellow dyes (yellow couplers), such as benzoylacetanilide or pivaloylacetanilide couplers, are described in British Pat. No. 1,113,038 and US. Pat. Nos.

3,337,344 and 3,582,322, and in addition, the followl CH3 0 ing couplers can also be used as the yellow coupler:

a- {3-[a-m-Pentadecylphenoxy)butyramido]benzoyl}-2-chloroacetanilide a-{3-[a-2,4-Di-t-amylphenoxy)butyramido]benzoyl}-2-methoxyacetanilide a-{3-[01-2,4-Di-t-amylphenoxy)acetamido]benzoyl}- 2-chloroacetanilide 2-Chloro-3 '-[4-( 2,4-di-t-amylphenoxy)butyramido]- benzoylacetanilide a-{3-[a-(2,4-Di-t-amylphenoxy)acetamido1benxoylbenzoylacetanilide a-Pivalyl-2,5-dichloro-4-[N'-(n-octadecyl)-N'- methylsulfamyl]acetanilide The above described compounds are examples of four-equivalent type yellow couplers which can be incorporated in photographic materials which can be treated according to this invention, and it is a matter of course that this invention is not limited to only the above-described couplers. These couplers often do not sufficiently color in a bleaching-fixation solution since a relatively stable leuco type structure occurs therebetween when a dye is formed by coupling, being different from other two-equivalent couplers. According to the steps of the method of this invention, however, even such couplers can fully be used for coloration, and in addition, the difficult problem of discharge of harmful substances is extremely improved.

It is a matter of course that photographic materials containing conventional two-equivalent couplers can be treated according to the method of this invention. Examples of such couplers are those as described in US. Pat. No. 3,582,322 and as described below,

CH -C-COCHCONH@ COOH Other examples of yellow couplers are given below. (X represents a group to be removed by coupling.)

, C 1 (CH3) cco iHc0NH- x NHCOCHO H (t) C ll mace/cu a (t) CH Cl 5 QcOTHCQNH- X cooc H C OCH -cocnconn COOC H (n) These couplers can be synthesized by conventional methods as described, for example, In U.S. Pat. Nos. 3,277,155 and 3,408,194; German Pat. (OLS) No. 2,057,941; U.S. Pat. Nos. 2,350,138, 2,359,332, 2,407,210, 2,875,057, 3,265,506, 3,341,331, 3,409,439, 3,551,155, 3,551,156, and 3,649,279; British Pat. No. 1,261,156 and U.S. Pat. No. 1,296,411.

Suitable examples of magenta dye forming couplers are disclosed in the hereinbefore described U.S. Pa-

tents.

Examples of cyan dye forming couplers are disclosed in the hereinbefore cited U.S. Patents and include the following specific examples.

-(p-Amylphenoxybenzenesulfoamido l -naphthol 5-(N-Benzyl-N-naphthalenesulfoamino)-l-naphthol 5 -(N-Benzyl-N-n-vale rylamino l -naphthol S-Caproylamino-l-naphthol 2-Chloro-5-(p-nitrobenzoyl-B-o-hydroxyethylamino 1 -naphthol 2-Chloro-5-palmytylamino-1-naphthol 2 ,2 '-Dihydroxy-5 ,5 '-dibromostylbene 5 -Diphenylethersulfoamido-1-naphthol 1-I-Iydroxy-2-(N-sec-amylphenyl )naphthamide S-Phenoxyacetamino-l-naphthol Monochloro-S-(N-y phenylpropyLN-p-sec-amylbenzoylamino )-1 -naphthol 2-Acetylamino-5-methylphenol 2-Benzoylamino-3,S-dimethylphenol 1 -Hydroxy-2- [a-( 2 ,4-di-t-amylphenoxy-n-butyl naphthamide 2-(4"-t-Amyl-3-phenoxybenzoylamino )phenol In addition, the compounds as described in U.S. Pat. No. 3,5 82,322 can also be utilized.

Silver halide emulsions thus prepared are applied and dried on a support such as glass, baryta paper, resin coated paper, cellulose acetate film or polyethylene terephthalate film using a dip method, an air-knife method, a bead method, an extrusion doctor method or a both surfaces, coating metho'd.

When the thus coated silver halide photographic materials are color photographicmaterials, the emulsion layer preferably comprises the three layers of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, and as the case may be, at least one of these layers can comprise a number of layer. For example, the green-sensitive emulsion layer can comprise two layers, e.g., a highly sensitive layer and low sensitive layer. It is a matter of course that conventional auxiliary layers which are generally well known in this field such as a protective layer, an intermediate layer, a filter layer, an anti-halation layer and a backing layer can optionally be added.

, The method of this invention can be applied to the processing of any and all conventional silver halide photographic materials where removal of silver is necessary, such as color negative films, color papers, color positive films, color reversal films for slides, color reversal films for television use and black-white reversal films. Suitable temperatures at which the bleaching method of this invention can be employed in the processing of silver halide photographic materials can range from about to 60C, preferably to 50C,

with a bleaching processing time of about seconds to 20 minutes, preferably 1 minute to 10 minutes.

According to the method of this invention, the toxicity of the bleaching agent used is low and the bleaching rate thereof is relatively high, and therefore, it is possible to carry out the bleaching step in a more stable manner as compared with other conventional bleaching agents. Accordingly, the time necessary for photographic processing is reduced and there is no danger of environmental pollution resulting from the discharged solution. It is a matter of course that color images fi-' nally obtained by the present method are free from any color fog and stain.

Another advantage attainable by the present method is that recovery and use of the fatigued bleaching solution are simplified. This is because bleaching agents of the kinds of the presentinvention can be recovered simply by blowing air or oxygen thereinto when fatigued, and therefore, recovery of silver is also easy. In view of the fact that such an advantage cannot be attained when conventional bleaching-fixation solutions are used, this advantage is considered an important additional merit of this invention.

When the bleaching solution of this invention is used, the bleaching ability thereof does not decrease even if the content of the silver halide or the silver iodide of the photographic material treated is increased. On the contrary, when a conventional non-toxic photographic bleaching agent such as a Fe(III)-aminopolycarboxylic acid complex is used, the bleaching ability thereof decreases if the content of silver halide or silver iodide is increased. In such case, although the content of silver halide or silver iodide is not critical, the standard content thereof is in general about 40 mg/lOO cm of silver EXAMPLE 1 l-I-lydroxy-4-chloro-2-m-dodecylnaphthamide as a,

cyan coupler was emulsified and mixed in a red-sensitive silver bromoiodide emulsion (Agl 7 mole%), and analogously, 1-(2',4,6-trichlorophenyl)-3-[3"-(2",- 4 '-di-t-amylphenoxyacetamido )benzamido -5 pyrazolone as a magenta coupler in a green-sensitive silver bromoiodide emulsion (Agl 6 mole%) and apyvalyl-a-[4-(4-benzyloxysulfonyl)phenoxy]-2-chloro- 5-[y-(2,4-di-t-amylphenoxy)-butylamido]acetanilide as a yellow coupler in a blue-sensitive silver bromoiodide (Agl 6 mole%), and these were applied on a triacetate film base to form a color negative photographic material, which was used in the following experiment.

In the emulsification of each couplerdibutyl phthalate and tricresyl phosphate were used as coupler solvents, sorbitan monolaurate and dodecylbenzene sodium sulfonate were used as emulsifiers, and in addition, l-( p-nonylphenoxy-trioxyethylene )-butane-4- sodium sulfonate and sucrose laurate were added as coating aids. After the film was exposed, the following Processing (1) was carried out.

Processmg (I) Color Development 24C 12 min. Stopiping Solution Bath 4 min Har ening Bath 4 min. Water Washing 4 min. Bleaching Bath 6 min. Water Washing 4 min. Fixation Bath 8 min. Water Washing 8 min. Drying 10 min. Color Developer Composition Benzyl Alcohol ml Sodium Hydroxide 0.5 g Diethyleneglycol 3 ml Sodium Hexametaphosphate 2 g Sodium Sulfite 2 g Potassium Bromide 2 g 4-Amino B-methyl-N-ethyl-B-hydroxy- 5 g ethylaniline-sesquisulfate-monohydrate Metaboric Acid 0.5 g Sodium Metaborate 77 g Water to make 1 liter Stopping Solution Sodium Acetate 30 g Glacial Acetic Acid 8 ml 1 liter Water to make Hardening Bath Sodium Hexametaphosphate l g Borax (5H O) 20 g Formalin (37%) ml Water to make 1 liter Bleaching Solution I Ferric Chloride (6H O) 30 g Tetrasodium Ethylenediaminetetraacetate 40 g Potassium Bromide 60 g Water to make 1 liter The pH was adjusted to 6.00 with acetic acid or aqueous ammonia.

Bleaching Solution ll fled dispersion, a silver bromochloride emulsion (silver chloride 70 mole containing a cyan coupler emulsifled dispersion, and a gelatin layer containing an ultraviolet absorbing agent, to prepare a color paper. Each coupler emulsion used in the preparation of this color paper was prepared as follows: Each coupler was dissolved in a mixture of dibutyl phthalate and tricresyl phosphate, and the resulting solution was dispersed in a gelatin solution in the form of an o/w dispersion using sorbitan monolaurate, Turkey red oil and dodecylbenzene sodium sulfonate as dispersing and emulsifying agents. As the couplers, l-(2',4,6'-trichlorophenyl)-3- [3 2' ,4' '-di-t-amylphenoxyacetamido )benzamido -5 -pyrazolone, l-( hydroxy )-4-chloro-2-ndodecylnaphthamide and a-(2-methylbenzoyl)-achloroaceto-( 2'-chloro-5 '-dodecoxycarbonyl )anilide were used. As the ultraviolet absorbing agent the compound described in US. Pat. No. 3,512,984 was used. In the emulsions was used 2,4-dichloro-6-hydroxy- 1,3,5-triazine sodium salt as a hardener. The thus prepared color paper sample was exposed using a color printer, and then the following color development processing was carried out.

Processing (II) Ferric Chloride (6H,O) Ethylenediamine-N,N,N',N'-tetramethylene 50 g Phosphonic Acid Potassium Bromide 60 g Water to make 1 liter The pH value was adjusted to 6.00 with acetic acid or aqueous ammonia.

Fixation Solution Sodium Thiosulfate l50 g Sodium Sulfite 15 g Borax 12 g Glacial Acetic Acid 15 ml Potassium Alum 20 g 1 liter Water to make EXAMPLE 2 On a baryta paper were applied a silver bromide emulsion containing a yellow coupler emulsified dispersion, a silver bromochloride emulsion (silver chloride 70 mole containing a magenta coupler emulsi- Processing Steps Temperature Time Color Development 30C 6 min. Stopping 2 min. Water Washing 2 min. Bleaching 2 min. Water Washing 2 min. Fixation 2 min. Water Washing 2 min. Stabilization Bath 2 min. Drying 2 min.

The treating solutions used had the following compositions:

COLOR DEVELOPER COMPOSITION Benzyl Alcohol 12 ml Diethyleneglycol 3.5 g Sodium Hydroxide 20 g Sodium Sultite 20 g Potassium Bromide 0.4 g Sodium Chloride 1.0 g Borax 4.0 g Hydroxylamine Sulfate 20 g Ethylenediaminetetraacetic Acid 20 g 4-Amino-3-methyl-N-ethyl-N-(B-sulfonamido- 50 g ethyl)aniline-sesquisulfate-monohydrate Water to make 1 liter Stopping Solution Sodium Thiosulfate 10 g Ammonium Thiosulfate 30 cc Sodium Acetate 5 g Acetic Acid 30 cc Potassium Alum 15 Water to make 1 fiter Bleaching Solution Ferric Chloride (6H,O) 30 g kHcyl'droxyethylidene-l,l-diphosphonic 25 g c1 Aqueous Ammonia (28%) 30 ml Ammonium Bromide 60 g Water to make 1 liter The pH was adjusted to 6.2 with acetic acid or aqueous ammonia.

Fixation Solution Sodium Thiosulfate g Sodium Sulfite 15 g Borax 12 g Glacial Acetic Acid 15 ml -continued Processing (III)-continued Potassium Alum 20 g Processing Steps Temperature Time Water to make 1 liter Stabilization Solution 5 g g aq p p -8 E Borie Acid 5 g co cc Sodium Citrate s g l g Sodium Tertiary Phosphate 40.0 g Sodium Metaborate 3 g P Potassium Alum 15 g otasslum q g water to make 1 liter Potassium Iodide (0.1% aqueous solution) 10.0 g Sodium Hydroxide 6.5 g 4-Amino-3-methyl-N-ethyl-N-methane- 10.0 g sulfonamidoethylaniline sulfate After the above described processing a color image agzgf'zg 'sgg f was obtained free from any color fog and stain where Bleaching Solutionl silver was completely removed. With bleaching solu- Potassium Ferricyanide 100 g tion of this example, there is no danger of environmen- Pmassmm Bmm'de Water to make 1 llter tal pollution, and the solution can be easily recovered, Bleaching solution H when fatigued, by blowing air thereinto. Thus, the Ferric chloride 5, 54 g bleaching solution is stable for a long period of time. z t g -NN y Phosphonic 70 2 CI Aqueous Ammonia 30 ml EXAMPLE 3 Ammonium Bromide 100 g l-Hydroxy-4-chloro-2-n-dodecylnaphthamide as a make I 1 cyan coupler was emulsified and mixed in a red-sensitive silver bromoiodide emulsion (AgI 7 mole and analogously 1423436gmchlomphenynsq3n4n di The pH was ad usted to 5.8 with acetic acid or aquet-amylphenoxyacetamido)-benzamido]-5-pyrazolone ous ammomaas a magenta coupler in a green-sensitive silver bromo- Fi i l i iodide (AgI 6 mole and a-[2-methylbenzoyl1- aceto-(2-chloro-5'-dodecoxycarbonyl)-anilide as a gg 'g g i8 5 yellow coupler m a blue-sensitive silver bromoiodide Water to make 1 liter emulsion (AgI 6 mole and these were applied on a polyethylene terephthalate film to prepare a color reversal photographic material, which was then exposed After the above processing color images were obusing a sensitometer and processed according to the tained free from any color fog and stain where silver is following Processing (III). completely removed, with both Bleaching Solution I Processing (1) and Bleaching Solution II. When these bleaching soluv tions were fatigued, however, Bleaching Solution II was Prosessmg Step5 Tempeame easily regenerated simply by blowing air thereinto and Pro-hardening 317C 2 min. and 30 secthe regenerated solution could be used analogously to a g fgfgtfigg fresh solution, but Bleaching Solution I cannot be re- First Sto pin 30 sec. generated by such simple treatment. In addition, the wine wash'ng 1 40 potassium ferricyanide used in the preparation of Color Development 3 min. and 30 sec. second stoppmg sec, Bleaching Solution I gives rise to extreme environmen- Wate' ,Washiflg 1 i tal pollution if the solution thereof is discharged, but Bleaching 3 min. Fixation 1 mm there IS no such danger with Bleaching Solution II. Water Washing l min. EEC? processing slolution has the following composition:

reardening oution Formalin-(37% aqueous solution) 20 cc EXAMPLE 4 gL g fl i The following bleaching solution was used and othersodium sun-ate 100 g wise the same process as in Example 2 was carried out. Potassium Bromide 2 g Borax 5 g Water 9 "l l lief Bleaching Solution Composition Neutralization Solution 1 Potassium Bromide 20 g Cobalt Acetate 24 g Glacial Acetic A id 10 cc Ethylened amlne-N,N,N',N-tetramethylene 40 g Sodium Sulfate 50 g Phosphonlc Ac|d Sodiu Hydroxide 6 g Aqueous Ammonia 30 ml Glycine 10 Ammonium Bromide g Water to make 1 fiter Water to make 1 liter First Developer Soglium lI-I3exametaIljtosphate g en razolone sodium sulgi s() g The pH was ad usted to 6.2 with acetic acid oraque- Hydroquinone 6.0 g ous m Sodium Carbonate (H O) 35.0 g 60 A a moma potassium g id m g nalogously to Example 2, an excellent color image 5 x 3 fz yi g g I -8 s free from color fog and stain was obtained where the f i'fg' g e aquems 1 fif silver was completely removed. First Stopping Solution and Second Stopping Solution While the invention has been described in detail and acetic Alcid s f 25 cc with reference to specific embodiments thereof, it will g L K$$ ate g be apparent to one skilled in the art that various Water to make 1 iter changes and modifications can be made therein with- Color Developer out departing from the spirit and scope thereof.

What is claimed is:

1. In a method for developing, bleaching and fixing an image-wise exposed silver halide photographic material, bleaching and fixing comprising separate steps in said method, the improvement comprising bleaching the silver halide photographic material with a bleaching solution containing a polyvalent cation-organic phosphonic acid complex as the bleaching agent and a rehalogenating agent selected from the group consisting of an alkali metal halide and an ammonium halide.

2. The method as claimed in claim 1, wherein said polyvalent cation is Fe(lIl), Co, Ni or Cu(ll).

3. The method as claimed in claim 1, wherein said organic phosphonic acid is an aminopolymethylene phosphonic acid or a water-soluble salt thereof.

4. The method as claimed in claim 3, wherein said aminopolymethylene phosphonic acid is represented by the following general formula (I) R|N(CHZPO3M)Z (I) where M represents a hydrogen atom or a cation which imparts water-solubility; R represents an alkyl group having 1 to 4 carbon atoms; an aryl group; an aralkyl group; an alicyclic group; or a heterocyclic group.

5. The method as claimed in claim 4, wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion; wherein the alkyl group for R is a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group; wherein said aryl group for R is a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a p-carboxyphenyl group, or a water-soluble salt of a p-carboxyphenyl group; wherein said aralkyl group for R is a benzyl group, an a-phenyl group or an o-acetamidobenzyl group; wherein said alicyclic. group for R is a cyclohexyl group or a cyclopentyl group; and wherein said heterocyclic group for R is a pyrrolidylmethyl group, a pyrrolidylbutyl group, a benzothiazolymethyl group or a tetrahydroquinolylmethyl group. v v

6. The method as claimed in claim 4, wherein R is an alkyl group substituted with a hydroxyl group, an alkoxyl group, a halogen atom, -PO M CH PO M or N(CH PO N wherein M represents a hydrogen atom or a cation which imparts water-solubility.

7. The method as claimed in claim 1, wherein said organic phosphonic acid is a compound respresentably the general formula (II) A z a a :)2 where R represents a hydrogen atom or an alkyl group, an aralkyl group, an alicyclic group or a heterocyclic group, or PO M and R represents a hydrogen atom, a hydroxyl group, an alkyl group, -PO M wherein M is a hydrogen atom or a cation which im- 36' parts water-solubility. solubility.

8. The method as claimed in claim 7, wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion; wherein the alkyl group for R is a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group.

9. The method as claimed in claim 7, wherein the alkyl group for R is an alkyl group substituted with a hydroxyl group, an alkoxyl group, a halogen atom, PO M CH -PO M or N(CH PO N wherein M is a hydrogen atom or a cation which imparts water-solubility.

10. The method as claimed in claim 4 wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion. a

11. The method as claimed in claim 6 wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion.

12. The method as claimed in claim 7 wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion.

13. The method as claimed in claim 9 wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion.

14. The method as claimed in claim 1, wherein said aminopolymethylene phosphonic acid is selected from those represented by the following general formulae (l) or II i 2 a z)z where M represents a hydrogen atom or a cation which imparts water-solubility; R represents an alkyl group having 1 to 4 carbon atoms; an aryl group; an aralkyl group; an alicyclic group; or a heterocyclic group; or

R2R3C( 1303M; (ll) where R represents a hydrogen atom or an alkyl group, an aralkyl group, an alicyclic group or a heterocyclic group, or PO M and R represents a hydrogen atom, a hydroxyl group, an alkyl group, -PO M wherein M is a hydrogen atom or a cation which imparts water-solubility.

15. The method as claimed in claim 14 wherein said polyvalent cation is Fe(IlI), Co, Ni or Cu(lI).

16. The method as claimed in claim 15 wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion.

17. The method as claimed in claim 1 wherein from about 20 to 200 g. of said polyvalent cation-organic phosphonic acid complex is present per one liter of the bleaching solution.

18. The method as claimed in claim 1 wherein said bleaching solution has a pH of about 3 to 8. 

1. IN A METHOD FOR DEVELOPING, BLEACHING AND FIXING AN IMAGE-WISE EXPOSED SILVER HAIDE PHOTOGRAPHIC MATERIAL BLEACHING AND FIXING COMPRISING SEPARATE STEPS IN SAID METHOD THE IMPROVEMENT COMPRISING BLEACHING THE SILVER HALIDE PHOTOGRAPHIC MATERIAL WITH A BLEACHING SOLUTION CONTAINING A POLYVALENT CATION-ORGANIC PHOSPHONIC ACID COMPLEX AS THE BLEACHING AGENT AND A RE-HALOGENATING AGENT SELECTED FROM THE GROUP CONSISTING OF AN ALKALI METAL HALIDE AND AN AMMONIUM HALIDE.
 2. The method as claimed in claim 1, wherein said polyvalent cation is Fe(III), Co, Ni or Cu(II).
 3. The method as claimed in claim 1, wherein said organic phosphonic acid is an aminopolymethylene phosphonic acid or a water-soluble salt thereof.
 4. The method as claimed in claim 3, wherein said aminopolymethylene phosphonic acid is represented by the following general formula (I) R1N(CH2PO3M2)2 (I) where M represents a hydrogen atom or a cation which imparts water-solubility; R1 represents an alkyl group having 1 to 4 carbon atoms; an aryl group; an aralkyl group; an alicyclic group; or a heterocyclic group.
 5. The method as claimed in claim 4, wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion; wherein the alkyl group for R1 is a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group; wherein said aryl group for R1 is a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a p-carboxyphenyl group, or a water-soluble salt of a p-carboxyphenyl group; wherein said aralkyl group for R1 is a benzyl group, an Alpha -phenyl group or an o-acetamidobenzyl group; wherein said alicyclic group for R1 is a cyclohexyl group or a cyclopentyl group; and wherein said heterocyclic group for R1 is a pyrrolidylmethyl group, a pyrrolidylbutyl group, a benzothiazolymethyl group or a tetrahydroquinolylmethyl group.
 6. The method as claimed in claim 4, wherein R1 is an alkyl group substituted with a hydroxyl group, an alkoxyl group, a halogen atom, -PO3M2, -CH2 PO3M2 or -N(CH2PO3N2)2, wherein M represents a hydrogen atom or a cation which imparts water-solubility.
 7. The method as claimed in claim 1, wherein said organic phosphonic acid is a compound respresentably the general formula (II) R2R3C(PO3M2)2 (II) where R2 represents a hydrogen atom or an alkyl group, an aralkyl group, an alicycliC group or a heterocyclic group, or -PO3M2 and R3 represents a hydrogen atom, a hydroxyl group, an alkyl group, -PO3M2, wherein M is a hydrogen atom or a cation which imparts water-solubility. solubility.
 8. The method as claimed in claim 7, wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion; wherein the alkyl group for R2 is a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group.
 9. The method as claimed in claim 7, wherein the alkyl group for R2 is an alkyl group substituted with a hydroxyl group, an alkoxyl group, a halogen atom, -PO3M2, -CH2-PO3M2 or -N(CH2PO3N2)2, wherein M is a hydrogen atom or a cation which imparts water-solubility.
 10. The method as claimed in claim 4 wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion.
 11. The method as claimed in claim 6 wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion.
 12. The method as claimed in claim 7 wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion.
 13. The method as claimed in claim 9 wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion.
 14. The method as claimed in claim 1, wherein said aminopolymethylene phosphonic acid is selected from those represented by the following general formulae (I) or (II) R1N(CH2PO3M2)2 (I) where M represents a hydrogen atom or a cation which imparts water-solubility; R1 represents an alkyl group having 1 to 4 carbon atoms; an aryl group; an aralkyl group; an alicyclic group; or a heterocyclic group; or R2R3C(PO3M2)2 (II) where R2 represents a hydrogen atom or an alkyl group, an aralkyl group, an alicyclic group or a heterocyclic group, or -PO3M2, and R3 represents a hydrogen atom, a hydroxyl group, an alkyl group, -PO3M2, wherein M is a hydrogen atom or a cation which imparts water-solubility.
 15. The method as claimed in claim 14 wherein said polyvalent cation is Fe(III), Co, Ni or Cu(II).
 16. The method as claimed in claim 15 wherein M is an alkali metal, ammonium or water-soluble substituted ammonium ion.
 17. The method as claimed in claim 1 wherein from about 20 to 200 g. of said polyvalent cation-organic phosphonic acid complex is present per one liter of the bleaching solution.
 18. The method as claimed in claim 1 wherein said bleaching solution has a pH of about 3 to
 8. 